JP5595491B2 - COMPOSITE CARBON MATERIAL INCREASING MIXTURE, CONTINUOUS MANUFACTURING METHOD, AND APPARATUS - Google Patents
COMPOSITE CARBON MATERIAL INCREASING MIXTURE, CONTINUOUS MANUFACTURING METHOD, AND APPARATUS Download PDFInfo
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Description
【技術分野】
【０００１】
本発明は、炭素ナノチューブ複合素材及びその製造方法に関し、炭素ナノチューブ、炭素ナノチューブ以外の１種以上の炭素化合物及び分散媒を含む混合物が亜臨界または超臨界条件において生成され、相互混和性が増大した炭素ナノチューブ複合素材及びこれを連続的に製造する方法に関する。
【背景技術】
【０００２】
炭素ナノチューブ（Carbon nanotube；ＣＮＴ）は、１９９１年その構造が初めて発見され、これに関する合成と物性、そして応用に関する研究が活発に行われている。また、ＣＮＴは、電気放電時Ｆｅ、Ｎｉ、Ｃｏなどのような遷移金属を添加すれば生成されることが確認され、本格的な研究は、１９９６年レーザー蒸発法によって相当量の試料を作り出してから始まった。このようなＣＮＴは、グラファイト（Graphite）面がナノサイズの直径で丸く巻いた中が空いたチューブ形態であり、この際、グラファイト面が巻かれた角度及び構造によって電気的特性が導体または半導体などになる。また、ＣＮＴは、グラファイト壁の数によって、単一壁の炭素ナノチューブ（Single-walled carbon nanotube；ＳＷＣＮＴ）、二重壁の炭素ナノチューブ（Double-walled carbon nanotube；ＤＷＣＮＴ）、薄壁の炭素ナノチューブ（Thin multi-walled carbon nanotube）、多重壁の炭素ナノチューブ（Multi-walled carbon nanotube；ＭＷＣＮＴ）、束状の炭素ナノチューブ（Roped carbon nanotube）に区分する。
【０００３】
特に、ＣＮＴは、機械的強度及び弾性度に優れ、化学的に安定しており、環境親和性を有しており、電気的に導体及び半導体性を有するのみならず、直径が１ｎｍから数十ｎｍであり、長さが数μｍから数十μｍで、縦横比が約１，０００に至る既存の如何なる物質よりも大きい。また、比表面積が非常に大きくて、将来の次世代の情報電子素材、高効率エネルギー素材、高能性の複合素材、親環境素材などの分野において２１世紀を担う先端の新素材として脚光を浴びている。
【０００４】
このような炭素ナノチューブは、現在ポリマーだけでなく、セラミック、金属などの基材において伝導性及び強化材料として利用されており、これに関する研究も活発に行われている。特に、炭素ナノチューブをポリマーなどの基材において伝導性などの物性を向上させるための素材として用いる場合、単独で用いた時の原料（炭素ナノチューブ）の経済的負担及び劣悪な分散性などの問題を克服するために、他の素材との混合を介して高伝導性複合素材を製造し、高付加価値の材料として用いようとする試みがなされている。
【０００５】
これに対して、韓国の発明特許第７０６６５２号において、熱可塑性樹脂の８０乃至９９重量の炭素ナノチューブの０．１乃至１０重量部、及び有機ナノクレイの０．１乃至１０重量部を含む電気伝導性の熱可塑性樹脂組成物が提案された。
【０００６】
また、韓国の特許公開第２００６−５２６５７号において、Ａ）９９．６乃至１０重量部の一つの熱可塑性樹脂、Ｂ）０乃至５０重量部の一つ以上のゴム−弾性重合体、Ｃ）０．２乃至１０．０重量部の炭素ナノフィブリル、Ｄ）０．２乃至１０．０重量部の一つ以上の微粒子炭素化合物、好ましくはカーボンブラックまたは黒鉛粉末、Ｅ）０乃至５０重量部の一つ以上の充填剤及びまたは強化物質を含む組成物が提案された。
【０００７】
しかし、前記特許方法は、炭素ナノチューブの性能を最大限に発揮するために炭素ナノチューブを基材内に分散することに依然として困難があり、電気伝導の流れを形成するには、複合素材の相互混和性が欠けているため、所望の伝導性を得るために炭素ナノチューブ及び複合素材が必要以上に用いられる可能性があり、この場合、むしろ基材の物性を悪化させる恐れがある。
【先行技術文献】
【特許文献】
【０００８】
【特許文献１】韓国特許第７０６６５２号
【特許文献２】韓国特許公開第２００６−５２６５７号
【発明の概要】
【発明が解決しようとする課題】
【０００９】
上記のような問題点を解決するために、本発明の目的は、炭素ナノチューブ、炭素ナノチューブ以外の１種以上の炭素化合物及び分散媒を含む混合物を亜臨界または超臨界条件において処理し、混和性または分散性を増大させることにより、少量の添加で基材内において分散性に優れ伝導性が向上した炭素ナノチューブ複合素材及びその製造方法を提供することにある。
【課題を解決するための手段】
【００１０】
上記目的を達成するために本発明は、炭素ナノチューブ、炭素ナノチューブ以外の１種以上の炭素化合物及び分散媒を含む混合物を５０乃至４００ａｔｍの亜臨界または超臨界条件において処理して生成された炭素ナノチューブ複合素材及びその製造方法とその装置を提供する。本発明による炭素ナノチューブ複合素材及びその製造方法は、亜臨界または超臨界条件において処理することにより、相互混和性及び結合力を増大させ、分散性に優れ伝導性が向上した炭素ナノチューブ複合素材が提供できるという長所がある。
【００１１】
より具体的に、本発明は、前記混合物を亜臨界または超臨界条件において処理することにより、相互混和性または分散性が増大されることができる。また、酸化剤をさらに含む場合、前記酸化剤が前記混合物の粒子間に均一に浸透して表面を均一な濃度に酸化されるようにし、酸化剤を含んで亜臨界または超臨界処理をした場合、前記酸化剤の浸透力がさらに優れたものとなり、酸化反応がより均一で早く進む。従って、本発明による炭素ナノチューブ複合素材は、前記酸化反応により、相互結合力及び混和性がより増加することができる。相互混和性が増大した炭素ナノチューブ複合素材は、少量を添加してもポリマーなどの基材における分散性及び伝導性に優れるという長所がある。以下、本発明による炭素ナノチューブ複合素材に関してより詳細に説明する。
【００１２】
本発明において、前記炭素化合物は、黒鉛、炭素繊維、カーボンブラック、グラフェン、フラーレン及びこれらの混合物からなる群から選ばれたものを用いることが好ましく、前記炭素ナノチューブは、単一壁（Single-walled）、二重壁（Double-walled）、薄い多重壁（Thin multi-walled）、多重壁（Multi-walled）、束状（Roped）及びこれらの混合物からなる群から選ばれることが好ましい。前記炭素ナノチューブと炭素化合物との混和性を効果的に増大させるのに好ましい重量比の範囲は、１：０．００００１〜１：１００であり、これに大きく制限されない。
【００１３】
発明において用いられる前記分散媒は、水、脂肪族アルコール、二酸化炭素及びこれらの混合物からなる群から選ばれてもよい。
【００１４】
本発明による前記炭素ナノチューブ複合素材は、相互混和性が増大されることにより、表面抵抗を減少させる効果を有することができ、下記式１を満たすことができる。
【００１５】
［式１］
１×１０２Ω／□≦Ｒｐ≦１×１０８Ω／□
（前記Ｒｐは、前記炭素ナノチューブ複合素材が４重量％含まれたポリエチレン樹脂の表面抵抗である。）
【００１６】
前記混合物は、前記亜臨界または超臨界条件において酸化剤をさらに含んで処理したものであり、前記酸化剤は、酸素、空気、オゾン、硝酸、過酸化水素、及びこれらの混合物から選ばれてもよく、炭素ナノチューブ及び炭素化合物１００重量部に対して０．００００１乃至３０重量部を含むことが好ましい。
【００１７】
以下、本発明による炭素ナノチューブ複合素材の製造方法を下記図面を参照してより詳細に説明する。
【００１８】
本発明は、炭素ナノチューブ、炭素ナノチューブ以外の１種以上の炭素化合物及び分散媒を含む混合物を５０乃至４００ａｔｍの亜臨界または超臨界条件において処理して生成された炭素ナノチューブ複合素材の製造方法を提供し、より具体的には、
ａ）炭素ナノチューブ、炭素ナノチューブ以外の１種以上の炭素化合物及び分散媒を含む混合物を１乃至４００ａｔｍの圧力で予熱槽に注入して予熱する段階と、
ｂ）前記予熱された混合物を５０乃至４００ａｔｍの亜臨界または超臨界条件において処理する段階と、
ｃ）前記ｂ）段階の生成物を０乃至１００℃に冷却及び１乃至１０ａｔｍに減圧する段階と、
ｄ）前記冷却／減圧された生成物を回収する段階と、
を含む炭素ナノチューブ複合素材製造方法を提供する。
【００１９】
前記混合物は、前記亜臨界または超臨界条件において酸化剤をさらに含んで処理してもよく、前記酸化剤は、酸素、空気、オゾン、硝酸、過酸化水素及びこれらの混合物から選ばれてもよい。また、前記酸化剤は、炭素ナノチューブ及び炭素化合物１００重量部に対して０．００００１乃至３０重量部を含んでもよい。前記酸化剤及び分散媒に対する具体的な説明は前記言及したため省略する。
【００２０】
また、本発明は、炭素ナノチューブと、炭素ナノチューブ以外の、１種以上の炭素化合物及び分散媒を含む混合物を１乃至４００ａｔｍの圧力で注入する予熱槽と、前記予熱槽を経た混合物が５０乃至４００ａｔｍで亜臨界または超臨界の処理を行う混和性増大のための反応槽と、前記混和性増大のための反応槽を経た混合物を０乃至１００℃に冷却して、１乃至１０ａｔｍに減圧する冷却／減圧槽と、前記冷却／減圧槽を経て生成物が回収される生成物貯蔵槽と、で構成される連続的に混合物の相互混和性または分散性を増大させる装置を提供する。
【００２１】
以下、本発明に添付された図面を参照して本発明の好ましい一実施例を詳細に説明する。先ず、図面のうち、同一の構成要素または部品は、できる限り同一の参照符号を示していることに留意しなければならない。本発明を説明するにおいて、関連の公知機能あるいは構成に対する具体的な説明は、本発明の要旨を曖昧にしないために省略する。
【００２２】
本明細書に用いられる程度を表す用語「約」、「実質的に」などは、言及された意味に固有の製造及び物質の許容誤差が提示される際、その数値またはその数値に近い意味で用いられ、本発明の理解を容易にするために正確または絶対的な数値が言及された開示内容を非良心的な侵害者が不当に利用することを防止するために用いられる。
【００２３】
下記図１は、本発明による炭素ナノチューブ複合素材の製造過程を示したものであり、下記図２は、本発明の好ましい一実施例による炭素ナノチューブ複合素材の製造過程をより具体的に示した工程図である。
【００２４】
図２を参照すると、本発明は、混合段階Ｓ１００と、予熱段階Ｓ２００と、混和性増大段階Ｓ３００と、冷却／減圧段階Ｓ４００と、生成物回収段階Ｓ５００と、を含む炭素ナノチューブ複合素材の製造方法を提供する。また冷却／減圧後に濾過段階Ｓ４１０をさらに含むことができる。
【００２５】
図３は、本発明の好ましい一実施例による炭素ナノチューブ複合素材を製造するための装置の工程図である。図３を参照すると、本発明の工程は、混合槽１０と、予熱槽１１０と、混和性増大のための反応槽１３０と、冷却／減圧槽１５０と、生成物貯蔵槽１７０と、が含まれることができる。
【００２６】
前記ａ）段階において、炭素ナノチューブ、炭素ナノチューブ以外の１種以上の炭素化合物及び分散媒を含む混合物は、予熱槽１１０に注入される前に混合槽１０に投入され、循環ポンプ１１によって混合物に製造される混合段階Ｓ１００を経る。前記混合物は、炭素ナノチューブ及び炭素ナノチューブ以外の１種以上の炭素化合物を０．０００１乃至３０重量％含んでもよく、より好ましくは、０．００１乃至５重量％を含んでもよい。
【００２７】
前記炭素ナノチューブ及び炭素化合物が全体混合物において０．０００１重量％未満である場合、生成物の回収量が非常に少なくなり、３０重量％を超える場合、前記混合物の粘度上昇で高圧の注入が難しい。
【００２８】
前記ａ）段階において予熱Ｓ２００は、前記予熱槽１１０で行われ、前記混合物を１乃至４００ａｔｍの圧力で注入して予熱してもよい。
【００２９】
前記混合物が、１乃至４００ａｔｍ圧力で高圧ポンプ１２を介して予熱槽１１０に投入される過程において、酸化剤を酸化剤の高圧注入ポンプ１３を介して１乃至４００ａｔｍの圧力でさらに投入されてもよく、前記混合物を酸化剤と接触して熱交換器１４前端で前記混合物と酸化剤とがともに混合されて予熱槽１１０に投入され、予熱槽において５０乃至３７０℃で予熱される。前記高圧注入ポンプ１３を介して混合物と酸化剤とが注入される際、圧力が１ａｔｍ未満である場合、混合物と酸化剤が予熱槽１１０及び反応槽１３０に注入されにくく、４００ａｔｍを超えると、非常に高い圧力によりエネルギー損失がもたらされる可能性があり、亜臨界または超臨界処理時に反応性がそれ以上向上しない。
【００３０】
前記予熱槽１１０は、前記混合物が以下の亜臨界または超臨界条件において処理される前に予め予熱して反応槽１３０の温度を一定に保持するためのものである。従って、前記予熱槽１１０の前端に熱交換器１４を設けて前記混合物及び酸化剤を予熱させる役割を果たし、熱交換器１４は、亜臨界または超臨界処理された生成物を冷却させる前にまず温度を下げて以後の冷却時に、消費されるエネルギー損失を防止する役割を行う。前記予熱槽の温度が５０℃未満の場合、以後の亜臨界または超臨界処理の際に温度をさらに高くあげるようになってエネルギー損失の防止効果がなく、３７０℃を超えると、予熱の効果よりは温度をあげるエネルギー損失がかえって増加するため、熱交換器の設置の効果がなくなる可能性がある。前記予熱段階Ｓ２００の後、混和性増大段階Ｓ３００を経るが、前記混和性増大段階は亜臨界または超臨界処理をする段階を意味する。前記予熱槽１１０において予熱された混合物と酸化剤は、反応槽１３０に移送されて５０乃至４００ａｔｍの亜臨界または超臨界条件において処理してもよい。
【００３１】
前記反応槽１３０の温度は、大きく制限されないが、５０乃至６００℃であることが好ましい。より詳細には、前記亜臨界処理の際の温度は、５０乃至３８０℃が好ましく、１００乃至３５０℃がさらに好ましい。亜臨界処理の際の圧力は５０乃至２６０ａｔｍが好ましく、６０乃至２６０ａｔｍがさらに好ましい。この際の処理時間は０．１分乃至６０分であることが好ましく、１分乃至２０分であることがさらに好ましい。
【００３２】
一方、前記超臨界処理時の圧力は、１５０乃至４００ａｔｍが好ましく、２１０乃至３００ａｔｍがさらに好ましい。温度は、３５０乃至６００℃であることが好ましく、３７０乃至５００℃がさらに好ましい。この際の処理時間は、０．１分乃至６０分間であることが好ましく、１分乃至１５分間であることがさらに好ましい。
【００３３】
この際、前記反応槽１３０において亜臨界または超臨界処理後に生成された生成物は、熱交換器１４を経て１００乃至３７０℃になるように１次冷却をしてもよく、前記１次冷却は、連続的に注入されて予熱された混合物及び酸化剤の予熱温度により、１次冷却を行ってもよい。また、連続的に投入された混合物及び酸化剤の予熱源は、反応槽１３０で処理された生成物により予熱されてもよく、これによってエネルギー損失が防止ができるという長所がある。
【００３４】
前記亜臨界または超臨界処理後に生成された生成物は、冷却／減圧段階Ｓ４００を経て０乃至１００℃及び１乃至１０ａｔｍで冷却／減圧されてもよい。前記熱交換器１４によって１次冷却された生成物は冷却装置１５を介して冷却してもよい。前記冷却温度は３０乃至５０℃に調節することが好ましい。
【００３５】
前記冷却された生成物は、まず前記冷却された生成物の冷却された状態を保持したまま冷却／減圧槽１５０でキャピラリー減圧装置で１０乃至１００ａｔｍに先に減圧し、圧力調節装置１６で１乃至１０ａｔｍに最終減圧する。
【００３６】
前記冷却／減圧を経た生成物を最終的に生成物貯蔵槽１７０に回収する段階Ｓ５００が行なわれることができる。前記生成物は液状でも利用できるが、粉末形態でも利用することができる。前記粉末形態の生成物を得るために、前記ｃ）段階後に生成物を高圧濾過させる段階である濾過段階Ｓ４１０をさらに含んでもよい。
【００３７】
下記図４は、本発明の好ましい一実施例による炭素ナノチューブ複合素材を連続的に製造するための濾過装置が含まれた装置工程図である。前記亜臨界または超臨界処理を行って冷却した生成物を濾過させるため、０．００１乃至１０μｍの空隙を有する高圧フィルターが並列に連結されてスイッチングモードで運転される濾過槽２１０、２３０がさらに含まれる。前記濾過槽２１０、２３０を介して濾過液２１１、２３１と濾過生成物２１３、２３３に分離排出され、前記濾過液２１１、２３１は濾過圧力調節装置１６を通じて常圧状態に減圧されて濾過液貯蔵槽３００に移送されて処理される。前記濾過槽２１０、２３０は必要容量に応じて１つ以上並列に設置できる。
【００３８】
より具体的に、前記並列に連結された濾過槽２１０、２３０で混和性が向上した濾過生成物と濾過液に分離される際、前記濾過槽２１０に圧力がかかると、バルブを締めて濾過槽２３０を開け前記冷却した生成物を濾過させ、これと同時に、濾過槽２１０内の濾過生成物２１３を回収し、濾過液２１１は濾過液貯蔵槽３００に移送されて処理される。
【００３９】
前記と同一の方法で濾過槽２３０に圧力がかかると、バルブを締めて、濾過槽２１０に取り替えてこれを開けて連続的に冷却された生成物を濾過させ、濾過槽２３０内の濾過生成物２３３が回収され、濾過液２３１は、濾過液貯蔵槽３００に移送されて処理される過程を繰り返して交互にスイッチングモードで濾過させることによって連続的な炭素ナノチューブ複合素材を製造するだけでなく、混和性をさらに増大させることができる。
【００４０】
本発明はまた前記本発明によって製造された炭素ナノチューブ複合素材及び熱可塑性樹脂を含む樹脂組成物を提供する。
【００４１】
前記樹脂組成物は、発泡剤をさらに含むことを特徴とし、前記発泡剤は大きく制限されないが、アゾジカルボキシルアミド、アゾビステトラゾールジアミノグアニジン、アゾビステトラゾールグアニジン、５−フェニルテトラゾール、ビステトラゾールグアニジン、ビステトラゾールピペラジン、ビステトラゾールジアンモニウム、Ｎ，Ｎ−ジニトロソペンタメチレンテトラミン、ヒドラゾジカルボキシルアミド及びこれらの混合物から選択されて用いることが好ましい。
【００４２】
本発明において、前記熱可塑性樹脂は、ポリエチレン系樹脂、ポリアセタール系樹脂、ポリアクリレート系樹脂、ポリカーボネート系樹脂、ポリスチレン系樹脂、ポリエステル系樹脂、ポリビニル系樹脂、ポリフェニレンエーテル系樹脂、ポリオレフィン系樹脂、ポリアクリロニトリル−ブタジエン−スチレン共重合体樹脂、ポリアリレート系樹脂、ポリアミド系樹脂、ポリアミドイミド系樹脂、ポリアリールスルホン系樹脂、ポリエーテルイミド系樹脂、ポリエーテルスルホン系樹脂、ポリフェニレンスルフィド系樹脂、ポリフッ素系樹脂、ポリイミド系樹脂、ポリエーテルケトン系樹脂、ポリベンゾオキサゾール系樹脂、ポリオキサジアゾール系樹脂、ポリベンゾチアゾール系樹脂、ポリベンゾイミダゾール系樹脂、ポリピリジン系樹脂、ポリトリアゾール系樹脂、ポリピロリジン系樹脂、ポリジベンゾフラン系樹脂、ポリスルホン系樹脂、ポリウレア系樹脂、ポリホスファゼン系樹脂からなる群から選ばれた一つまたは二つ以上の混合物を用いてもよい。
【００４３】
本発明によって製造された炭素ナノチューブ複合素材を含む前記樹脂組成物は、伝導性塗料、静電分散材、静電分散塗料、伝導性素材、電磁波遮蔽材、電磁波吸収材、電磁波遮蔽塗料、電磁波吸収塗料、太陽電池用材料、色素増感太陽電池（ＤＳＳＣ）用電極材料、電気素子、電子素子、半導体素子、光電素子、ノートパソコン部品材料、コンピュータ部品材料、携帯電話部品材料、ＰＤＡ（personal digital assistants）部品材料、ゲーム機用部品材料、ハウジング材料、透明電極材料、不透明電極材料、電界放出ディスプレイ（field emission display；ＦＥＤ）材料、バックライトユニット（back light unit；ＢＬＵ）材料、液晶表示装置（liquid crystal display；ＬＣＤ）材料、プラズマ表示パネル（plasma display panel；ＰＤＰ）材料、発光ダイオード（luminescent diode；ＬＥＤ）材料、タッチパネル材料、電光板材料、広告看板材料、ディスプレイ素材、発熱体、放熱体、メッキ材料、触媒、助触媒、酸化剤、還元剤、自動車部品材料、船舶部品材料、航空機部品材料、デジタル封筒材料、保護テープ材料、接着剤材料、トレイ材料、クリーンルーム材料、運送機器部品材料、難燃素材、抗菌素材、金属複合材料、非鉄金属複合材料、医療機器部品材料、建材、床仕上げ材料、壁紙材料、光源部品材料、ランプ材料、光学機器部品材料、繊維製造機器部品材料、衣類製造機器部品材料、電気製品製造機器材料、電子製品製造機器材料からなる群から選ばれた一つ以上の材料に用いることができる。前記本発明におけるデジタル封筒は、各種の電子製品の帯電防止及び水分からの保護のために用いられる包装材を意味する。
【発明の効果】
【００４４】
本発明による炭素ナノチューブ複合素材及びその製造方法は、亜臨界または超臨界条件において処理することにより、相互混和性、分散性及び結合力を増大させ、分散性に優れ伝導性が向上した炭素ナノチューブ複合素材が提供できるという長所がある。また、取り扱い及び廃水処理が容易であり、有害でない酸化剤をさらに含み、連続的な装置を通じて製造することにより、相互混和性、分散性及び結合力をさらに増大することができるという長所がある。
【００４５】
本発明による炭素ナノチューブ複合素材は、多様な種類の溶媒及び高分子樹脂の基材により、従来に比べ高い分散性及び有機的結合力を有することができ、これにより電気伝導性、熱伝導性、強度、耐磨耗性、耐衝撃性、弾性及び発泡性の多様な物性を向上することができる。
【００４６】
また、本発明により製造された炭化ナノチューブ複合素材を含む樹脂組成物は、伝導性塗料、静電分散材、静電分散塗料、伝導性素材、電磁波遮蔽材、電磁波吸収材、電磁波遮蔽塗料、電磁波吸収塗料、太陽電池用材料、色素増感太陽電池（ＤＳＳＣ）用電極材料、電気素子、電子素子、半導体素子、光電素子、ノートパソコン部品材料、コンピュータ部品材料、携帯電話部品材料、ＰＤＡ（personal digital assistants）部品材料、ゲーム機用部品材料、ハウジング材料、透明電極材料、不透明電極材料、電界放出ディスプレイ（field emission display；ＦＥＤ）材料、バックライトユニット（back light unit；ＢＬＵ）材料、液晶表示装置（liquid crystal display；ＬＣＤ）材料、プラズマ表示パネル（plasma display panel；ＰＤＰ）材料、発光ダイオード（luminescent diode；ＬＥＤ）材料、タッチパネル材料、電光板材料、広告看板材料、ディスプレイ素材、発熱体、放熱体、メッキ材料、触媒、助触媒、酸化剤、還元剤、自動車部品材料、船舶部品材料、航空機部品材料、デジタル封筒材料、保護テープ材料、接着剤材料、トレイ材料、クリーンルーム材料、運送機器部品材料、難燃素材、抗菌素材、金属複合材料、非鉄金属複合材料、医療機器部品材料、建材、床仕上げ材料、壁紙材料、光源部品材料、ランプ材料、光学機器部品材料、繊維製造機器部品材料、衣類製造機器部品材料、電気製品製造機器材料、電子製品製造機器材料からなる群から選ばれる一つ以上の材料に用いることができるため、多様な分野において高付加価値材料として用いることができるという長所がある。
【図面の簡単な説明】
【００４７】
【図１】本発明による炭素ナノチューブ複合素材の製造過程を示した図面である。
【図２】本発明の好ましい一実施例による炭素ナノチューブ複合素材の製造過程を示した図面である。
【図３】本発明の好ましい一実施例による炭素ナノチューブ複合素材の製造の連続的な製造装置の工程図である。
【図４】本発明の好ましい一実施例による濾過装置が含まれた炭素ナノチューブ複合素材の製造の連続的な製造装置の工程図である。
【図５ａ】実施例１によって製造された炭素ナノチューブ複合素材の走査型電子顕微鏡写真である。
【図５ｂ】比較例１における多重壁炭素ナノチューブとカーボンブラック混合物の走査型電子顕微鏡写真である。
【図６ａ】実施例３によって製造された炭素ナノチューブ複合素材の透過型電子顕微鏡写真である。
【図６ｂ】比較例１の多重壁の炭素ナノチューブ及びカーボンブラック混合物の透過型電子顕微鏡写真である。
【発明を実施するための形態】
【００４８】
下記の実施例を通じてより詳細に説明する。
【実施例１】
【００４９】
多重壁の炭素ナノチューブ（ハンファナノテク社製ＭＷＣＮＴ）１０ｇとカーボンブラック（アメリカCabot社製Carbon-black）１０ｇとを蒸留水９８０ｇと循環ポンプ１１で混合して混合槽１０で混合物を準備した。前記混合物を高圧注入ポンプ１２を介して１５ｇ／ｍｉｎ流速で予熱槽１１０に投入した。前記溶液は、熱交換器１４を介して２００乃至２４０℃で予熱された予熱槽１１０に投入した。
【００５０】
前記予熱された混合物は、３００℃及び２３０ａｔｍ乃至２５０ａｔｍの亜臨界状態の混和性増大のために反応槽１３０に注入して反応槽内で亜臨界処理されるとともに相互混和性が増大され、前記混和性が増大した生成物は、また熱交換器１４に移送されて２００℃で１次冷却され、再び冷却装置１５を介して約２５℃の温度に冷却された後、連続的に相互混和性が増大した１９．９ｇの炭素ナノチューブ複合素材を得た。
【００５１】
［参考例１］
多重壁の炭素ナノチューブとカーボンブラックの炭素ナノチューブ複合素材の予熱の際に、熱交換器１４の温度が３５０乃至３７０℃であることと、超臨界において温度を４００℃に処理し、相互混和性を増大させたことを除いて、前記実施例１と同様に実施し、１９．２ｇの炭素ナノチューブ複合素材生成物を得た。
【実施例３】
【００５２】
酸素を２４５ａｔｍ乃至２５２ａｔｍに圧縮された気象状態で熱交換器１４の前端で０．０４ｇ／ｍｉｎの流速で注入して多重壁の炭素ナノチューブとカーボンブラック混合物と混合して予熱槽１１０に投入することを除いて、前記実施例１と同様に実施し、１９．２ｇの炭素ナノチューブ複合素材生成物を得た。
【実施例４】
【００５３】
前記実施例１と同様に実施し、カーボンブラックの代わりにカーボンファイバー（日本東レ社製carbon-fiber）を用いたことを除いて、前記実施例１と同様に反応して相互混和性が増大した１９．９ｇの炭素ナノチューブ複合素材生成物を得た。
【実施例５】
【００５４】
回転する二軸圧出機のホッパー（hopper）に、９６０ｇの低密度のポリエチレン（ＬＤＰＥ８３０；ＨＣＣ）と、実施例１の方法により製造された４０ｇの炭素ナノチューブ複合素材とを投入した。２００℃の圧出機軸の回転によって高分子樹脂が応用され、炭素ナノチューブ複合素材と混練し、圧出機ダイ（die）を介して連続的に排出するようにした。圧出機から排出されるポリエチレン束（strand）をペレタイザー（pelletizer）を利用して通常の短いペレット（pellet）に製造した後、前記ペレットをプレスを利用して厚さ２ｍｍのシートを製造した。
【実施例６】
【００５５】
実施例３の方法により製造された炭素ナノチューブ複合素材４０ｇを用いたことを除いて、前記実施例５と同様に実施した。
【実施例７】
【００５６】
実施例４の方法により製造された炭素ナノチューブ複合素材４０ｇを用いたことを除いて、前記実施例５と同様に実施した。
【００５７】
[比較例１]
１対１に混合した多重壁の炭素ナノチューブ（ハンファナノテク社製ＭＷＣＮＴ）及びカーボンブラック（アメリカCabot社製Carbon-black）混合物を一般の電動ミキサー（Electric-mixer；SHINIL社製ELECTRIC MIXER、ＳＦＭ−１５００ＮＭ）を利用して１分間分散させた後、ホッパーに直接投入したことを除いて、実施例５と同様に実施した。
【００５８】
[比較例２]
１対１に混合した多重壁の炭素ナノチューブ（ハンファナノテク社製ＭＷＣＮＴ）及びカーボンファイバー（日本東レ社製carbon-fiber）複合炭素素材の原料を一般の電動ミキサー（Electric-mixer；SHINIL社製ELECTRIC MIXER、ＳＦＭ−１５００ＮＭ）を利用して１分間分散させた後、ホッパーに直接投入したことを除いて、実施例５と同様に実施した。
【００５９】
[試験例]
１．走査型電子顕微鏡（Scanning Electron Microscope；ＳＥＭ）観察
走査型電子顕微鏡は、Hitachi社製Ｓ４８００モデルであり、実施例１及び比較例１によって製造された炭素ナノチューブ複合素材を水に分散させ、ガラス上に落としてから完全に乾燥させた後、白金でメッキした後測定した。
【００６０】
下記図５ａは、前記実施例１の走査型電子顕微鏡を通じて観察した写真であって、前記実施例１で製造された炭素ナノチューブ複合素材は、亜臨界の過程を経りながら混和性が増大し、前記多重壁の炭素ナノチューブとカーボンブラックが均一に分散されていることを示す。下記図５ｂは、前記比較例１の多重壁の炭素ナノチューブとカーボンブラック混合物を一般の電動ミキサー（Electric-mixer；SHINIL社製ELECTRIC MIXER、ＳＦＭ−１５００ＮＭ）を利用して、１分間分散させた後、走査型電子顕微鏡で観察した写真である。下記図５ａと比較した時、図５ｂは、多重壁の炭素ナノチューブとカーボンブラックが混和されず、ほとんど独立的に存在することを確認することができた。
【００６１】
２．透過型電子顕微鏡（Transmission Electron Microscope；ＴＥＭ）観察
透過型電子顕微鏡は、ＪＥＯＬ社のＪＥＭ−２１００Ｆ（ＨＲ）モデルであり、試料は、ホーリックタイプのグリッドの上で測定した。下記図６ａは、前記実施例３によって製造された炭素ナノチューブ複合素材を観察したものであって、前記実施例３で多重壁の炭素ナノチューブとカーボンブラックの混合物が亜臨界酸化過程を経りながら混和性が向上し、二つの炭素素材が均一に分散していることを示す。下記図６ｂは、比較例１の混合物を一般のホモミキサー（homo-mixer；SHINIL社製ELECTRIC MIXER、ＳＦＭ−１５００ＮＭ）を利用して１分間分散させた後、透過型電子顕微鏡で観察した写真である。下記図６ｂは、下記図６ａと比較して二つの炭素素材が混和されず、ほとんど独立的に存在することを確認することができる。
【００６２】
３．表面抵抗測定
実施例５、６、７と、比較例１、２の表面抵抗は、三菱社製Loresta ＧＰ（ＭＣＰ−Ｔ６００）を用いて、ＪＩＧ Ｋ ７１９４／ＡＳＴＭ Ｄ９９１によって測定し、その結果を下記表１に示した。
【００６３】
下記表１に示される、実施例５、６、７と、比較例１、２の表面抵抗を比較すると、混和性が増大した複合炭素素材が添加されたポリエチレンシートの表面抵抗がより低いということが分かる。
【００６４】
【表１】
【符号の説明】
【００６５】
１０ 混合槽
１１ 循環ポンプ
１２ 混合物高圧ポンプ
１３ 酸化剤高圧注入ポンプ
１４ 熱交換器
１５ 冷却装置
１６ 圧力調節装置
１１０ 予熱槽
１３０ 反応槽
１５０ 冷却／減圧槽
１７０ 貯蔵槽
２１０ 濾過槽
２１１ 濾過液
２１３ 亜臨界または超臨界処理及び濾過後の濾過生成物
２３０ 濾過槽
２３１ 濾過液
２３３ 亜臨界または超臨界処理及び濾過後の濾過生成物
３００ 濾過液貯蔵槽
【Technical field】
[0001]
The present invention relates to a carbon nanotube composite material and a method for producing the same, and a mixture containing carbon nanotubes, one or more types of carbon compounds other than carbon nanotubes and a dispersion medium is generated in subcritical or supercritical conditions, and the mutual miscibility is increased. The present invention relates to a carbon nanotube composite material and a method for continuously producing the same.
[Background]
[0002]
The structure of carbon nanotube (CNT) was first discovered in 1991, and research on the synthesis, physical properties, and application of this structure has been actively conducted. In addition, it is confirmed that CNTs are produced by adding transition metals such as Fe, Ni, Co, etc. during electrical discharge, and full-scale research has produced a considerable amount of samples by the laser evaporation method in 1996. It started from. Such a CNT is in the form of a tube in which a graphite (Graphite) surface is rolled with a nano-sized diameter and has a hollow inside. At this time, depending on the angle and structure around which the graphite surface is wound, the electrical characteristics may be a conductor or a semiconductor. become. In addition, CNTs have a single-walled carbon nanotube (SWCNT), a double-walled carbon nanotube (DWCNT), and a thin-walled carbon nanotube (Thin) depending on the number of graphite walls. It is divided into multi-walled carbon nanotubes, multi-walled carbon nanotubes (MWCNT), and bundled carbon nanotubes.
[0003]
In particular, CNTs have excellent mechanical strength and elasticity, are chemically stable, have environmental compatibility, have electrical conductivity and semiconducting properties, and have a diameter of 1 nm to several tens. It is larger than any existing material with a length of several μm to several tens of μm and an aspect ratio of about 1,000. In addition, it has a very large specific surface area, and has attracted attention as a leading new material for the 21st century in the fields of future next-generation information electronic materials, high-efficiency energy materials, high-performance composite materials, and environmentally friendly materials. Yes.
[0004]
Such carbon nanotubes are currently used not only as a polymer but also as a conductive and reinforcing material in substrates such as ceramics and metals, and research on this is being actively conducted. In particular, when carbon nanotubes are used as a material for improving physical properties such as conductivity in a substrate such as a polymer, problems such as the economic burden of raw materials (carbon nanotubes) and poor dispersibility when used alone In order to overcome this problem, attempts have been made to produce highly conductive composite materials through mixing with other materials and use them as high-value-added materials.
[0005]
In contrast, according to Korean Patent No. 7066652, electrical conductivity containing 80 to 99 parts by weight of carbon nanotubes of 0.1 to 10 parts by weight of carbon nanotubes and 0.1 to 10 parts by weight of organic nanoclays. A thermoplastic resin composition was proposed.
[0006]
In Korean Patent Publication No. 2006-52657, A) 99.6 to 10 parts by weight of one thermoplastic resin, B) 0 to 50 parts by weight of one or more rubber-elastic polymers, C) 0 .2 to 10.0 parts by weight of carbon nanofibrils, D) 0.2 to 10.0 parts by weight of one or more particulate carbon compounds, preferably carbon black or graphite powder, E) 0 to 50 parts by weight of one Compositions comprising one or more fillers and / or reinforcing materials have been proposed.
[0007]
However, the above-mentioned patented method still has difficulty in dispersing the carbon nanotubes in the substrate in order to maximize the performance of the carbon nanotubes. Due to the lack of properties, carbon nanotubes and composite materials may be used more than necessary to obtain the desired conductivity. In this case, the physical properties of the substrate may rather be deteriorated.
[Prior art documents]
[Patent Literature]
[0008]
[Patent Document 1] Korean Patent No. 706652
[Patent Document 2] Korean Patent Publication No. 2006-52657
SUMMARY OF THE INVENTION
[Problems to be solved by the invention]
[0009]
In order to solve the above-described problems, the object of the present invention is to treat a mixture containing carbon nanotubes, one or more carbon compounds other than carbon nanotubes, and a dispersion medium in subcritical or supercritical conditions, and miscibility. Alternatively, an object of the present invention is to provide a carbon nanotube composite material that is excellent in dispersibility and improved in conductivity in a base material by increasing the dispersibility and a method for producing the same.
[Means for Solving the Problems]
[0010]
In order to achieve the above object, the present invention relates to a carbon nanotube produced by treating a mixture containing carbon nanotubes, one or more carbon compounds other than carbon nanotubes, and a dispersion medium under subcritical or supercritical conditions of 50 to 400 atm. A composite material, a manufacturing method thereof, and an apparatus thereof are provided. The carbon nanotube composite material and the manufacturing method thereof according to the present invention provide a carbon nanotube composite material that has improved dispersibility and improved conductivity by increasing the mutual miscibility and bonding force by processing under subcritical or supercritical conditions. There is an advantage that you can.
[0011]
More specifically, according to the present invention, the miscibility or dispersibility can be increased by treating the mixture in subcritical or supercritical conditions. Further, when the oxidant is further included, the oxidant is uniformly between the particles of the mixturePenetrationWhen the surface is oxidized to a uniform concentration and the sub-critical or supercritical treatment is performed with an oxidant, the oxidant has a better permeability and the oxidation reaction proceeds more uniformly and quickly. . Therefore, the carbon nanotube composite material according to the present invention can further increase the mutual bonding force and miscibility due to the oxidation reaction. The carbon nanotube composite material having increased mutual miscibility has an advantage of being excellent in dispersibility and conductivity in a substrate such as a polymer even when a small amount is added. Hereinafter, the carbon nanotube composite material according to the present invention will be described in more detail.
[0012]
In the present invention, the carbon compound is preferably selected from the group consisting of graphite, carbon fiber, carbon black, graphene, fullerene and a mixture thereof, and the carbon nanotube is a single-walled ), Double-walled, thin multi-walled, multi-walled, bundled, and mixtures thereof. A preferable weight ratio range for effectively increasing the miscibility of the carbon nanotube and the carbon compound is 1: 0.00001 to 1: 100, but is not limited to this.
[0013]
The dispersion medium used in the invention may be selected from the group consisting of water, aliphatic alcohols, carbon dioxide, and mixtures thereof.
[0014]
The carbon nanotube composite material according to the present invention can have an effect of reducing surface resistance by increasing mutual miscibility, and can satisfy the following formula 1.
[0015]
[Formula 1]
1 × 102Ω / □ ≦ Rp≦ 1 × 108Ω / □
(RpIs the surface resistance of a polyethylene resin containing 4% by weight of the carbon nanotube composite material. )
[0016]
The mixture is further processed by further containing an oxidizing agent under the subcritical or supercritical conditions, and the oxidizing agent may be selected from oxygen, air, ozone, nitric acid, hydrogen peroxide, and a mixture thereof. It is preferable to contain 0.00001 to 30 parts by weight with respect to 100 parts by weight of the carbon nanotube and the carbon compound.
[0017]
Hereinafter, a method for producing a carbon nanotube composite material according to the present invention will be described in more detail with reference to the following drawings.
[0018]
The present invention provides a method for producing a carbon nanotube composite material produced by treating a carbon nanotube, a mixture containing one or more carbon compounds other than carbon nanotubes, and a dispersion medium under subcritical or supercritical conditions of 50 to 400 atm. And more specifically,
a) preheating by injecting a mixture containing carbon nanotubes, one or more carbon compounds other than carbon nanotubes, and a dispersion medium into a preheating tank at a pressure of 1 to 400 atm;
b) treating the preheated mixture at subcritical or supercritical conditions of 50 to 400 atm;
c) cooling the product of step b) to 0 to 100 ° C. and depressurizing to 1 to 10 atm;
d) recovering the cooled / depressurized product;
A method for producing a carbon nanotube composite material containing
[0019]
The mixture may be further treated with an oxidant in the subcritical or supercritical conditions, and the oxidant may be selected from oxygen, air, ozone, nitric acid, hydrogen peroxide, and mixtures thereof. . The oxidizing agent may include 0.00001 to 30 parts by weight with respect to 100 parts by weight of the carbon nanotube and the carbon compound. The specific explanation for the oxidizing agent and the dispersion medium is omitted because it has been mentioned above.
[0020]
In addition, the present invention provides a preheating tank in which a mixture containing carbon nanotubes and one or more carbon compounds other than carbon nanotubes and a dispersion medium is injected at a pressure of 1 to 400 atm, and a mixture having passed through the preheating tank has 50 to 400 atm. A reaction vessel for increasing miscibility in which a subcritical or supercritical treatment is carried out at a temperature, and a cooling / cooling in which the mixture that has passed through the reaction vessel for increasing miscibility is cooled to 0 to 100 ° C. and depressurized to 1 to 10 atm. There is provided an apparatus for continuously increasing the mutual miscibility or dispersibility of a mixture composed of a decompression tank and a product storage tank in which a product is recovered through the cooling / decompression tank.
[0021]
Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. First, it should be noted that in the drawings, the same components or parts are denoted by the same reference numerals as much as possible. In describing the present invention, specific descriptions of related known functions or configurations are omitted so as not to obscure the subject matter of the present invention.
[0022]
As used herein, the terms “about”, “substantially” and the like indicate the numerical value, or a meaning close to that numerical value, when manufacturing and material tolerances inherent in the meaning mentioned are presented. It is used to prevent the unfair infringer from making unauthorized use of disclosures that are used to facilitate understanding of the present invention and that are referred to with exact or absolute numerical values.
[0023]
FIG. 1 shows a process for manufacturing a carbon nanotube composite material according to the present invention, and FIG. 2 shows a process more specifically showing a process for manufacturing a carbon nanotube composite material according to a preferred embodiment of the present invention. FIG.
[0024]
Referring to FIG. 2, the present invention provides a method of manufacturing a carbon nanotube composite material including a mixing step S100, a preheating step S200, a miscibility increasing step S300, a cooling / depressurizing step S400, and a product recovery step S500. I will provide a. Further, it may further include a filtration step S410 after cooling / depressurization.
[0025]
FIG. 3 is a process diagram of an apparatus for manufacturing a carbon nanotube composite material according to a preferred embodiment of the present invention. Referring to FIG. 3, the process of the present invention includes a mixing tank 10, a preheating tank 110, a reaction tank 130 for increasing miscibility, a cooling / decompression tank 150, and a product storage tank 170. be able to.
[0026]
In the step a), a mixture containing carbon nanotubes, one or more carbon compounds other than carbon nanotubes, and a dispersion medium is charged into the mixing tank 10 before being injected into the preheating tank 110, and produced into a mixture by the circulation pump 11. The mixing step S100 is performed. The mixture may contain 0.0001 to 30% by weight, more preferably 0.001 to 5% by weight of carbon nanotubes and one or more carbon compounds other than carbon nanotubes.
[0027]
When the carbon nanotubes and the carbon compound are less than 0.0001% by weight in the total mixture, the amount of product recovered becomes very small, and when the amount exceeds 30% by weight, high-pressure injection is difficult due to the increase in viscosity of the mixture.
[0028]
In step a), the preheating S200 may be performed in the preheating tank 110, and the mixture may be preheated by being injected at a pressure of 1 to 400 atm.
[0029]
In the process in which the mixture is charged into the preheating tank 110 via the high-pressure pump 12 at a pressure of 1 to 400 atm, an oxidant may be further charged at a pressure of 1 to 400 atm via the high-pressure injection pump 13 of oxidant. The mixture is brought into contact with an oxidant, and the mixture and the oxidant are mixed together at the front end of the heat exchanger 14 and charged into the preheating tank 110, and preheated at 50 to 370 ° C. in the preheating tank. When the mixture and the oxidant are injected through the high-pressure injection pump 13, if the pressure is less than 1 atm, the mixture and the oxidant are difficult to be injected into the preheating tank 110 and the reaction tank 130. High pressure can lead to energy loss, and the reactivity is not further improved during subcritical or supercritical processing.
[0030]
The preheating tank 110 is used to preheat the mixture before it is processed under the following subcritical or supercritical conditions to keep the temperature of the reaction tank 130 constant. Accordingly, a heat exchanger 14 is provided at the front end of the preheating tank 110 to play a role of preheating the mixture and the oxidant. The heat exchanger 14 firstly cools the subcritical or supercritical processed product before cooling. It plays the role of preventing energy loss during cooling after lowering the temperature. When the temperature of the preheating tank is less than 50 ° C., the temperature is further increased during the subsequent subcritical or supercritical processing, and there is no effect of preventing energy loss. However, there is a possibility that the effect of installing the heat exchanger may be lost because the energy loss that raises the temperature increases. The preheating step S200 is followed by a miscibility increasing step S300. The miscibility increasing step means a subcritical or supercritical process. The mixture and oxidant preheated in the preheating tank 110 may be transferred to the reaction tank 130 and processed under subcritical or supercritical conditions of 50 to 400 atm.
[0031]
The temperature of the reaction vessel 130 is not greatly limited, but is preferably 50 to 600 ° C. More specifically, the temperature during the subcritical treatment is preferably 50 to 380 ° C, and more preferably 100 to 350 ° C. The pressure during the subcritical treatment is preferably 50 to 260 atm, and more preferably 60 to 260 atm. The treatment time at this time is preferably 0.1 to 60 minutes, more preferably 1 to 20 minutes.
[0032]
On the other hand, the pressure during the supercritical treatment is preferably 150 to 400 atm, and more preferably 210 to 300 atm. The temperature is preferably 350 to 600 ° C, more preferably 370 to 500 ° C. The treatment time at this time is preferably 0.1 to 60 minutes, more preferably 1 to 15 minutes.
[0033]
At this time, the product generated after the subcritical or supercritical treatment in the reaction vessel 130 may be subjected to primary cooling so as to be 100 to 370 ° C. through the heat exchanger 14, The primary cooling may be performed according to the preheated temperature of the continuously injected and preheated mixture and the oxidizing agent. In addition, the preheated source of the mixture and the oxidizing agent that are continuously charged may be preheated by the product processed in the reaction vessel 130, which has the advantage that energy loss can be prevented.
[0034]
The product generated after the subcritical or supercritical treatment may be cooled / depressurized at 0 to 100 ° C. and 1 to 10 atm through the cooling / depressurization step S400. The product primarily cooled by the heat exchanger 14 may be cooled through a cooling device 15. The cooling temperature is preferably adjusted to 30 to 50 ° C.
[0035]
The cooled product is first decompressed to 10 to 100 atm by the capillary decompression device in the cooling / decompression tank 150 while maintaining the cooled state of the cooled product, and 1 to 1 by the pressure regulator 16. Final depressurization to 10 atm.
[0036]
The step S500 of finally recovering the cooled / depressurized product in the product storage tank 170 may be performed. The product can be used in liquid form, but can also be used in powder form. In order to obtain the product in powder form, it may further include a filtration step S410, which is a step of high-pressure filtration of the product after the step c).
[0037]
FIG. 4 is an apparatus process diagram including a filtration apparatus for continuously producing a carbon nanotube composite material according to a preferred embodiment of the present invention. Filtration in which a high-pressure filter having a gap of 0.001 to 10 μm is connected in parallel and operated in a switching mode in order to filter the cooled product by performing the subcritical or supercritical treatment.Tank 210 and 230 are further included. The filtrates 211 and 231 and the filtered products 213 and 233 are separated and discharged through the filtration tanks 210 and 230, and the filtrates 211 and 231 are reduced to a normal pressure state through the filtration pressure control device 16 to be stored in the filtrate storage tank. It is transferred to 300 and processed. One or more filtration tanks 210 and 230 may be installed in parallel according to the required capacity.
[0038]
More specifically, when the filtration tank 210 and 230 connected in parallel are separated into a filtered product and a filtrate having improved miscibility, when the pressure is applied to the filtration tank 210, the valve is closed and the filtration tank is closed. 230 is opened, the cooled product is filtered, and at the same time, the filtered product 213 in the filtering tank 210 is recovered, and the filtrate 211 is transferred to the filtrate storage tank 300 and processed.
[0039]
When pressure is applied to the filtration tank 230 in the same manner as described above, the valve is tightened, the filtration tank 210 is replaced and opened, and the continuously cooled product is filtered, and the filtration product in the filtration tank 230 is filtered. 233 is recovered, and the filtrate 231 is transferred to the filtrate storage tank 300 and processed in a repeated manner by alternately repeating the process in the switching mode to produce a continuous carbon nanotube composite material. Can be further increased.
[0040]
The present invention also provides a resin composition comprising a carbon nanotube composite material produced according to the present invention and a thermoplastic resin.
[0041]
The resin composition further includes a foaming agent, and the foaming agent is not largely limited, but azodicarboxylamide, azobistetrazole diaminoguanidine, azobistetrazole guanidine, 5-phenyltetrazole, bistetrazole guanidine, It is preferably used by being selected from bistetrazole piperazine, bistetrazole diammonium, N, N-dinitrosopentamethylenetetramine, hydrazodicarboxylamide, and mixtures thereof.
[0042]
In the present invention, the thermoplastic resin is a polyethylene resin, polyacetal resin, polyacrylate resin, polycarbonate resin, polystyrene resin, polyester resin, polyvinyl resin, polyphenylene ether resin, polyolefin resin, polyacrylonitrile. -Butadiene-styrene copolymer resin, polyarylate resin, polyamide resin, polyamideimide resin, polyarylsulfone resin, polyetherimide resin, polyethersulfone resin, polyphenylene sulfide resin, polyfluorine resin , Polyimide resin, polyether ketone resin, polybenzoxazole resin, polyoxadiazole resin, polybenzothiazole resin, polybenzimidazole resin, polypyridine resin Polytriazoles resin, Poripirorijin resins, polychlorinated dibenzofurans resins, polysulfone resins, polyurea resins may be used one or two or more mixtures selected from the group consisting of polyphosphazene resin.
[0043]
The resin composition comprising the carbon nanotube composite material produced according to the present invention is a conductive paint, electrostatic dispersion material, electrostatic dispersion paint, conductive material, electromagnetic wave shielding material, electromagnetic wave absorbing material, electromagnetic wave shielding paint, electromagnetic wave absorption Paints, materials for solar cells, electrode materials for dye-sensitized solar cells (DSSC), electrical elements, electronic elements, semiconductor elements, photoelectric elements, notebook computer parts materials, computer parts materials, mobile phone parts materials, PDA (personal digital assistants) ) Part materials, game console parts materials, housing materials, transparent electrode materials, opaque electrode materials, field emission display (FED) materials, back light unit (BLU) materials, liquid crystal display devices (liquid) crystal display (LCD) material, plasma display panel (PDP) material, luminescent diode (luminescent) diode (LED) material, touch panel material, lightning board material, advertising billboard material, display material, heating element, heat radiator, plating material, catalyst, promoter, oxidizing agent, reducing agent, automotive parts material, ship parts material, aircraft parts Materials, digital envelope materials, protective tape materials, adhesive materials, tray materials, clean room materials, transportation equipment parts materials, flame retardant materials, antibacterial materials, metal composite materials, non-ferrous metal composite materials, medical equipment parts materials, building materials, floor finishing One or more selected from the group consisting of materials, wallpaper materials, light source component materials, lamp materials, optical device component materials, textile manufacturing device component materials, clothing manufacturing device component materials, electrical product manufacturing device materials, and electronic product manufacturing device materials It can be used for the material. The digital envelope in the present invention means a packaging material used for preventing various electronic products from being charged and protecting from moisture.
【Effect of the invention】
[0044]
The carbon nanotube composite material according to the present invention and the method for producing the same are processed under subcritical or supercritical conditions to increase the mutual miscibility, dispersibility, and bonding force, and the carbon nanotube composite has excellent dispersibility and improved conductivity. There is an advantage that material can be provided. In addition, it is easy to handle and treat wastewater, and further includes a non-hazardous oxidant, and can be manufactured through a continuous apparatus to further increase the mutual miscibility, dispersibility, and bonding strength.
[0045]
The carbon nanotube composite material according to the present invention can have higher dispersibility and organic bond strength than before due to various types of solvents and polymer resin base materials, thereby providing electrical conductivity, thermal conductivity, Various physical properties such as strength, abrasion resistance, impact resistance, elasticity, and foamability can be improved.
[0046]
In addition, the resin composition containing the carbonized nanotube composite material produced according to the present invention includes conductive paint, electrostatic dispersion material, electrostatic dispersion paint, conductive material, electromagnetic wave shielding material, electromagnetic wave absorbing material, electromagnetic wave shielding paint, electromagnetic wave Absorbent paints, materials for solar cells, electrode materials for dye-sensitized solar cells (DSSC), electrical elements, electronic elements, semiconductor elements, photoelectric elements, notebook computer parts materials, computer parts materials, mobile phone parts materials, PDA (personal digital) assistants) component materials, game console component materials, housing materials, transparent electrode materials, opaque electrode materials, field emission display (FED) materials, back light unit (BLU) materials, liquid crystal display devices ( liquid crystal display (LCD) material, plasma display panel (PDP) material, luminescent diode (luminescent) diode (LED) material, touch panel material, lightning board material, advertising billboard material, display material, heating element, heat radiator, plating material, catalyst, promoter, oxidizing agent, reducing agent, automotive parts material, ship parts material, aircraft parts Materials, digital envelope materials, protective tape materials, adhesive materials, tray materials, clean room materials, transportation equipment parts materials, flame retardant materials, antibacterial materials, metal composite materials, non-ferrous metal composite materials, medical equipment parts materials, building materials, floor finishing One or more materials selected from the group consisting of materials, wallpaper materials, light source component materials, lamp materials, optical device component materials, textile manufacturing device component materials, clothing manufacturing device component materials, electrical product manufacturing device materials, and electronic product manufacturing device materials Since it can be used as a material, it can be used as a high value-added material in various fields.
[Brief description of the drawings]
[0047]
FIG. 1 is a view showing a manufacturing process of a carbon nanotube composite material according to the present invention.
FIG. 2 is a view illustrating a manufacturing process of a carbon nanotube composite material according to a preferred embodiment of the present invention.
FIG. 3 is a process diagram of a continuous manufacturing apparatus for manufacturing a carbon nanotube composite material according to a preferred embodiment of the present invention.
FIG. 4 is a process diagram of a continuous production apparatus for producing a carbon nanotube composite material including a filtration apparatus according to a preferred embodiment of the present invention.
5a is a scanning electron micrograph of the carbon nanotube composite material produced according to Example 1. FIG.
5b is a scanning electron micrograph of a mixture of multi-walled carbon nanotubes and carbon black in Comparative Example 1. FIG.
6a is a transmission electron micrograph of a carbon nanotube composite material produced according to Example 3. FIG.
6b is a transmission electron micrograph of a mixed-wall carbon nanotube and carbon black mixture of Comparative Example 1. FIG.
BEST MODE FOR CARRYING OUT THE INVENTION
[0048]
This will be described in more detail through the following examples.
[Example 1]
[0049]
10 g of multi-walled carbon nanotubes (MWCNT manufactured by Hanwha Nanotech) and 10 g of carbon black (Carbon-black manufactured by Cabot, USA) were mixed with 980 g of distilled water and the circulation pump 11 to prepare a mixture in the mixing tank 10. The mixture was charged into the preheating tank 110 through the high-pressure injection pump 12 at a flow rate of 15 g / min. The solution was charged into a preheating tank 110 preheated at 200 to 240 ° C. via a heat exchanger 14.
[0050]
The preheated mixture is injected into the reaction vessel 130 to increase the miscibility in a subcritical state of 300 ° C. and 230 atm to 250 atm, and is subcritically treated in the reaction vessel and the mutual miscibility is increased. The product with increased properties is also transferred to the heat exchanger 14 where it is primarily cooled at 200 ° C. and again cooled to a temperature of about 25 ° C. via the cooling device 15 before being continuously intermiscible. An increased 19.9 g of carbon nanotube composite material was obtained.
[0051]
[Reference Example 1]
When preheating the multi-wall carbon nanotube and carbon black carbon nanotube composite material, the temperature of the heat exchanger 14 is 350 to 370 ° C. Except for the increase, the same procedure as in Example 1 was performed to obtain 19.2 g of a carbon nanotube composite material product.
[Example 3]
[0052]
Oxygen is injected at a flow rate of 0.04 g / min at the front end of the heat exchanger 14 in a weather state compressed to 245 atm to 252 atm, mixed with the multi-walled carbon nanotube and carbon black mixture, and charged into the preheating tank 110. Example 1 was carried out in the same manner as in Example 1 to obtain 19.2 g of a carbon nanotube composite material product.
[Example 4]
[0053]
The reaction was carried out in the same manner as in Example 1 except that carbon fiber (carbon-fiber manufactured by Nippon Toray Co., Ltd.) was used instead of carbon black. 19.9 g of carbon nanotube composite material product was obtained.
[Example 5]
[0054]
960 g of low density polyethylene (LDPE830; HCC) and 40 g of the carbon nanotube composite material produced by the method of Example 1 were charged into a hopper of a rotating biaxial extruder. The polymer resin was applied by rotating the extruder shaft at 200 ° C., kneaded with the carbon nanotube composite material, and continuously discharged through the extruder die. A polyethylene strand discharged from the press machine was manufactured into a normal short pellet using a pelletizer, and then the pellet was manufactured into a sheet having a thickness of 2 mm using a press.
[Example 6]
[0055]
The same operation as in Example 5 was performed except that 40 g of the carbon nanotube composite material produced by the method of Example 3 was used.
[Example 7]
[0056]
The same operation as in Example 5 was performed except that 40 g of the carbon nanotube composite material produced by the method of Example 4 was used.
[0057]
[Comparative Example 1]
Multi-walled carbon nanotubes (MWCNT manufactured by Hanwha Nanotech Co., Ltd.) and carbon black (Carbon-black manufactured by Cabot Inc., USA) mixed in a one-to-one relationship with a general electric mixer (Electric MIXER; SHINIL ELECTRIC MIXER, SFM-1500NM) ) Was dispersed for 1 minute, and then the same operation as in Example 5 was performed except that it was directly charged into the hopper.
[0058]
[Comparative Example 2]
Multi-walled carbon nanotubes (MWCNT manufactured by Hanwha Nanotech Co., Ltd.) and carbon fiber (carbon-fiber manufactured by Toray Industries, Inc.) mixed in a one-to-one basis. General electric mixer (Electric MIXER manufactured by SHINIL) , SFM-1500NM) for 1 minute, and then the same as Example 5 except that it was directly charged into the hopper.
[0059]
[Test example]
1. Scanning Electron Microscope (SEM) observation
The scanning electron microscope is an S4800 model manufactured by Hitachi, in which the carbon nanotube composite material produced in Example 1 and Comparative Example 1 was dispersed in water, dropped onto glass, dried completely, and then platinum. Measured after plating.
[0060]
FIG. 5a is a photograph observed through the scanning electron microscope of Example 1, wherein the carbon nanotube composite material produced in Example 1 has increased miscibility while undergoing a subcritical process. It shows that the multi-walled carbon nanotubes and carbon black are uniformly dispersed. FIG. 5b shows a case where the multi-wall carbon nanotube and carbon black mixture of Comparative Example 1 is dispersed for 1 minute using a general electric mixer (Electric MIXER, SFM-1500NM, manufactured by SHINIL). It is the photograph observed with the scanning electron microscope. When compared with FIG. 5a below, FIG. 5b confirmed that the multi-walled carbon nanotubes and carbon black were immiscible and exist almost independently.
[0061]
2. Transmission electron microscope (TEM) observation
The transmission electron microscope was a JEOL JEM-2100F (HR) model, and the sample was measured on a horic type grid. FIG. 6a is a view of the carbon nanotube composite material manufactured according to Example 3, in which a mixture of multi-walled carbon nanotubes and carbon black is mixed while undergoing a subcritical oxidation process. This shows that the two carbon materials are uniformly dispersed. FIG. 6b below is a photograph of the mixture of Comparative Example 1 observed with a transmission electron microscope after being dispersed for 1 minute using a general homomixer (ELECTRIC MIXER manufactured by SHINIL, SFM-1500NM). is there. FIG. 6b below can confirm that the two carbon materials are not mixed and exist almost independently compared to FIG. 6a below.
[0062]
3. Surface resistance measurement
The surface resistances of Examples 5, 6, and 7 and Comparative Examples 1 and 2 were measured by JIG K 7194 / ASTM D991 using a Loresta GP (MCP-T600) manufactured by Mitsubishi Corp. The results are shown in Table 1 below. Indicated.
[0063]
Comparing the surface resistances of Examples 5, 6, and 7 and Comparative Examples 1 and 2 shown in Table 1 below, the surface resistance of the polyethylene sheet added with the composite carbon material with increased miscibility is lower. I understand.
[0064]
[Table 1]
[Explanation of symbols]
[0065]
10 Mixing tank
11 Circulation pump
12 Mixture high pressure pump
13 Oxidant high-pressure injection pump
14 Heat exchanger
15 Cooling device
16 Pressure regulator
110 Preheating tank
130 reactor
150 Cooling / decompression tank
170 Storage tank
210 Filtration tank
211 Filtrate
213 Filtration product after subcritical or supercritical treatment and filtration
230 Filtration tank
231 Filtrate
233 Filtration product after subcritical or supercritical treatment and filtration
300 Filtrate storage tank
Claims (16)
前記炭素化合物が、カーボンブラック又は炭素繊維である、炭素ナノチューブ複合素材。 A composite material produced by treating a carbon nanotube, a mixture containing one or more carbon compounds other than carbon nanotubes, and a dispersion medium under subcritical conditions of 50 to 380 ° C. and 50 to 260 atm ,
A carbon nanotube composite material , wherein the carbon compound is carbon black or carbon fiber .
［式１］
１×１０２Ω／□≦Ｒｐ≦１×１０８Ω／□
（前記Ｒｐは、前記炭素ナノチューブ複合素材が４重量％含まれたポリエチレン樹脂の表面抵抗である。） The carbon nanotube composite material according to claim 1, wherein the carbon nanotube composite material satisfies the following formula 1.
[Formula 1]
1 × 10 2 Ω / □ ≦ R p ≦ 1 × 10 8 Ω / □
( Rp is the surface resistance of a polyethylene resin containing 4% by weight of the carbon nanotube composite material.)
前記炭素化合物が、カーボンブラック又は炭素繊維である、炭素ナノチューブ複合素材の製造方法。 A method for producing a composite material comprising treating a carbon nanotube, a mixture containing one or more carbon compounds other than carbon nanotubes, and a dispersion medium under subcritical conditions of 50 to 380 ° C. and 50 to 260 atm ,
A method for producing a carbon nanotube composite material, wherein the carbon compound is carbon black or carbon fiber .
Applications Claiming Priority (3)
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| KR10-2009-0059129 | 2009-06-30 | ||
| KR1020090059129A KR101470524B1 (en) | 2009-06-30 | 2009-06-30 | Blending improvement carbon-composite having Carbon-nanotube and its continuous manufacturing method |
| PCT/KR2010/004242 WO2011002222A2 (en) | 2009-06-30 | 2010-06-30 | Blending improvement carbon-composite having carbon-nanotube and its continuous manufacturing method and apparatus |
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| JP2014082603A Division JP5875622B2 (en) | 2009-06-30 | 2014-04-14 | COMPOSITE CARBON MATERIAL INCREASING MIXTURE, CONTINUOUS MANUFACTURING METHOD, AND APPARATUS THEREOF |
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| JP2014082603A Active JP5875622B2 (en) | 2009-06-30 | 2014-04-14 | COMPOSITE CARBON MATERIAL INCREASING MIXTURE, CONTINUOUS MANUFACTURING METHOD, AND APPARATUS THEREOF |
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2010
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| TW201105576A (en) | 2011-02-16 |
| EP2448862A2 (en) | 2012-05-09 |
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| JP2014205611A (en) | 2014-10-30 |
| EP2448862A4 (en) | 2014-10-22 |
| KR101470524B1 (en) | 2014-12-08 |
| WO2011002222A2 (en) | 2011-01-06 |
| CN102471049A (en) | 2012-05-23 |
| US9567222B2 (en) | 2017-02-14 |
| CN102471049B (en) | 2015-08-26 |
| CA2766987C (en) | 2015-12-15 |
| WO2011002222A3 (en) | 2011-04-14 |
| JP2012532085A (en) | 2012-12-13 |
| US20120112134A1 (en) | 2012-05-10 |
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